DL-N-benzoyl-2-(cyclopentadien-2-yl)glycine methyl ester

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: DL-N-benzoyl-2-(cyclopentadien-2-yl)glycine methyl ester
• 英文别名: Methyl 2-benzamido-2-cyclopenta-1,4-dien-1-ylacetate；methyl 2-benzamido-2-cyclopenta-1,4-dien-1-ylacetate
• 化学式: C₁₅H₁₅NO₃
• 分子量: 257.289
• InChiKey: AOWMYCRPKQISAC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  三甲硅烷基环戊二烯 、 N-benzoyl-2-bromoglycine methyl ester 在 zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 生成 DL-N-benzoyl-2-(cyclopentadien-2-yl)glycine methyl ester 、 DL-N-benzoyl-2-(cyclopentadien-1-yl)glycine methyl ester
  参考文献：
  名称：

  2-Cyclopentadienylglycine, a new α-amino acid and its use for η5-complex formation

  摘要：

  The reaction of alpha -bromohippuric acid methyl ester with nickelocene, cyclopentadienylthallium or cyclopentadienyltrimethylsilane afforded N-benzoyl-2-cyclopentadienylglycine methyl ester (1) as two double bond isomers 1a and 1b. Similarly, the cyclopentadienyl(Cp)-containing dipeptide Z-L-Phe-DL-(Cp)Gly-OMe (3) was obtained from Z-L-Phe-DL-Gly(Cl)-OMe and trimethylsilylcyclopentadiene. The amino acids 1a, 1b were susceptible to Diels-Alder cycloaddition and yielded dimer 2 as a mixture of regioisomers. Compound 1 and FeCl2 gave 1,1'-fenocenylene-bip(glycine) (5), whereas with [(COD)RhCl](2) rhodium eta (5)-cyclopentadienylglycine (6) and eta (5)-cyclopentadienyldipeptide complexes Like 7 were obtained from 1 or 3, respectively. Unexpectedly, the eta (5)-cyclopentadienylglycine complexes proved to be very sensitive to light. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00411-2

文献信息

• Cyclopentadienyl-Based Amino Acids (Cp-aa) As Phenylalanine Analogues for Tumor Targeting: Syntheses and Biological Properties of [(Cp-aa)M(CO)₃](M = Mn, Re, ^99mTc)
  作者：Samer Sulieman、Daniel Can、John Mertens、Harmel W. Peindy N’Dongo、Yu Liu、Paul Schmutz、Matthias Bauwens、Bernhard Spingler、Roger Alberto

  DOI：10.1021/om300695k

  日期：2012.10.8

  Due to an enhanced demand for amino acids, the L-type amino acid transporter 1 (LAT1) is overexpressed in many tumor cell lines. LAT1 represents therefore an attractive target for cancer therapy and diagnosis. On the basis of our reported aqueous synthesis of [(Cp-R)Tc-99m(CO)(3)]-type complexes,(1-S) we describe the preparation of unnatural amino acid analogues [(Cp-CH2CH(NH2)COOH)Mn(CO)(3)] and [(Cp-CH(NH2)COOH)M(CO)(3)] (M = Mn, Re, Tc-99m). Starting from fully protected HC5H5-aa (aa = amino acid), [(Cp-aa)Tc-99m(CO)(3)] complexes are accessible in quantitative yields and in a one-step synthesis from [(TcO4)-Tc-99m](-). The rhenium and manganese analogues were prepared and structurally characterized to confirm the authenticity of the Tc-99m complex. The inhibition constant of natural phenylalanine (phe) for LAT1 is in the range 70 +/- 10 mu M. The K-i value of [(Cp-CH(NH2)COOH)Mn(CO)(3)] (1a) is 53 +/- 11 mu M, whereas K-i for the "true" phe analogue [(Cp-CH2CH(NH2)COOH)Mn(CO)(3)] (2) was surprisingly high at 277 +/- 37 mu M. Complex la caused efflux when exposed to cells, underlining its active transport by LAT1 into the cell. Tc-99m analogues of small biological lead structures such as amino acids are generally not recognized anymore by their targets, in particular by trans-membrane transporters. The bioorganometallic analogues presented here are, however, actively transported and corroborate the importance of organometallic complexes as mimics of organic lead structures in life sciences.
• 2-Cyclopentadienylglycine, a new α-amino acid and its use for η5-complex formation
  作者：Harald Dialer、Wolfgang Steglich、Wolfgang Beck

  DOI：10.1016/s0040-4020(01)00411-2

  日期：2001.6

  The reaction of alpha -bromohippuric acid methyl ester with nickelocene, cyclopentadienylthallium or cyclopentadienyltrimethylsilane afforded N-benzoyl-2-cyclopentadienylglycine methyl ester (1) as two double bond isomers 1a and 1b. Similarly, the cyclopentadienyl(Cp)-containing dipeptide Z-L-Phe-DL-(Cp)Gly-OMe (3) was obtained from Z-L-Phe-DL-Gly(Cl)-OMe and trimethylsilylcyclopentadiene. The amino acids 1a, 1b were susceptible to Diels-Alder cycloaddition and yielded dimer 2 as a mixture of regioisomers. Compound 1 and FeCl2 gave 1,1'-fenocenylene-bip(glycine) (5), whereas with [(COD)RhCl](2) rhodium eta (5)-cyclopentadienylglycine (6) and eta (5)-cyclopentadienyldipeptide complexes Like 7 were obtained from 1 or 3, respectively. Unexpectedly, the eta (5)-cyclopentadienylglycine complexes proved to be very sensitive to light. (C) 2001 Elsevier Science Ltd. All rights reserved.